Ruthenium-Catalyzed Oxidative Heck Reactions

Abstract

Aryl boronic acids can undergo a Heck‐type reaction catalyzed by RuII in the presence of CuII, which serves as a reoxidant in each cycle (see scheme, step 1). Compatibility with halide substituents offers attractive synthetic potential (step 2).

Transition-Metal-Catalyzed Oxidative Heck Reactions

“…61,62 These investigations demonstrated that a ruthenium-carbon bond can be formed through a nucleophilic substitution and at the alkene insertion step. 63 Also, a major characteristic of ruthenium(II) chemistry is its inertness to organohalides under oxidative conditions. These features and observations may provide a promising opportunity to use ruthenium(II) complexes in the oxidative Heck reaction of haloboronic acids under reaction conditions for which it is generally impossible to effectively use palladium catalysts.…”

Catalysis and Organometallic Chemistry of Monometallic Species

“…Unusual ruthenium-catalysed oxidative Heck reactions have also have also been studied. 187 New classes of catalyst include a ruthenium() bis(N-heterocyclic carbene)pyridine for the hydrogenation of carbonyl compounds, 188 chiral ester functionalised Cp complexes of iron(), 189 and new ferrocenyl ligands exhibiting excellent enantioselectivities for asymmetric hydrogenation of amino acid synthesis. 190 A linkage isomer of decaphenyl ferrocene has been isolated and structurally characterised and contains η 5 -C 5 Ph 5 cyclopentadienyl and η 5/6 -C 5 Ph 5 arene coordination.…”

HOTf-Catalyzed Alkyl-Heck-type Reaction

“…The Heck reaction, pioneered by Heck and Mizoroki in the late 1960s and the early 1970s ( Heck, 1968 , Mizoroki et al., 1971 , Heck and Nolley, 1972 ), along with other cross-coupling reactions, led to a revolution in organic chemistry ( Johansson Seechurn et al., 2012 ). In the last 50 years, many types of Heck and Heck-type reactions, including metal-catalyzed ( Heck, 1968 , Mizoroki et al., 1971 , Heck and Nolley, 1972 , Littke and Fu, 2001 , Farrington et al., 2002 , Na et al., 2004 , Loska et al., 2008 , Delcamp et al., 2013 , Nishikata et al., 2013 , Standley and Jamison, 2013 ), photo-induced ( Iqbal et al., 2012 , Liu et al., 2013 , Paria et al., 2014 , Yu et al., 2014 ), or base-mediated ( Rueping et al., 2011 , Shirakawa et al., 2011 , Sun et al., 2011 ) reactions, have been elegantly developed ( Beletskaya and Cheprakov, 2000 , Dounay and Overman, 2003 , Wu et al., 2010 , Le Bras and Muzart, 2011 , Mc Cartney and Guiry, 2011 , Tang et al., 2015 ). Notwithstanding these classical reaction modes, there is no precedent of Brønsted acid-catalyzed or Brønsted acid-promoted Heck (or type) reaction being realized.…”